An efficient strategy for the cleavage of the C–N bond of tertiary amines was developed with DTBP as an oxidant, in which the cleaved H atom and amine moiety were successfully transferred to the desired products. This strategy has enabled an efficient palladium-catalyzed hydroaminocarbonylation of alkynes with tertiary amines. Notably, the catalyst loading could be lowered from 5 to 0.1 mol %, which represents the lowest catalyst loading among the reported work on carbonylation via C–N bond activation.